Refining of mineral oils



C512, 1943- G. E. PHILLIPS I REFINING OF MIiIERAL OILS Filed Dec. 17,1940 Patented Oct. 12,1943

UNITED STATES PATENT OFFICE 2,331,343 g REFINING OF MINERAD oILs- YGerald E. Phillips, Cranford, N. J., assignor to Standard OilDevelopment Company, a corporation of Delaware Application December 17,1940, Serial No. 370,461 9 Claims. (01. 196-28) The present inventionrelates to a process for ferred temperature. When operating in thisrefining mineral oils. The invention is more parmanner, a portion of theexothermic heat is ticularly concerned with the production of imtaken upby the feed stock and undesirable proved motor fuels having highanti-knocking degradation of the feed stock is prevented. It

scission of the same. However, due to the fact that the reaction whendesulfurizing oils of this character is exothermic, it has beenextremely difficult to maintain the temperature in the-reaction zonewithin the critical temperature range desired. 'In order to control thetemperature within the desired operating range, various proposals havebeen made. It has been proposed that the feed stock be introduced intothe bauxite-treating zone somewhat below the precharacteristics asmeasured by a high ,octane 5 has also been proposed to utilize variouscooling number, by an operation which comprises? bauxmeans, such ascooling coils and the like, ite-treating petroleum feed oils undercarefully throughout the reaction zone. This, however, controlledconditions.=s. In accordance with the has not been entirely satisfactorydue to the fact present invention, petroleum oils are processed that inorder adequately and positively to control under conditions adapted toproduce products the temperature of the reaction, the feed zone boilingin the motor fuel boiling range, which are must have a relatively smalldiameter. I have, characterized by having relatively highoctane however,now discovered a process by which it is numbers and relatively lowsulfur concentrations. possible to positively control the temperature ofThese products are produced by passing a suitthe reaction throughout thereaction zone within able feed oil through a bauxite bed within a thedesired narrow critical temperature range. critical temperature rangewhich is controlled by In accordance with my process, the temperatureintroducing, preferably at a plurality of stages, within the treatingzone is maintained substana liquid, preferably water, in relativelysmall tially constant by taking out the exothermic heat amounts. ofreaction by the use of a cooling liquid which It is known in the art tosubject various petrois preferably introduced at a plurality of stages.leum oil feed stocks, such as heavy naphthas, gas The process O yinvention y be readily oils, reduced crudes, and the like, totemperature n o d y reference t the attached r win and pressureconditions adapted to produce relaillustrating modifications of thesame. For purtively lower boiling constituents and relatively poses ofillustration, it is assumed that the feed higher boiling constituents.It is also known in oil comprises a cracked petroleum distillate boilheart to refine the resulting products by treating ins in the motor fuelboiling r nge. The feed oil the same with various acids, clays, metallics ntr d d t atin il or qu nt oxides, such as bauxite, and the like. Forexm a s I by m s f f d line n h at n ample, it is known to removeobjectionable sulfur ,coil l the feedoil is raised to the desiredtemcompounds from petroleum oils, particularly from Pe p f ly in the rane 01 about 700 F- petroleum oils boiling in the motor fuel boiling t0The feed 011 is Withdrawn by means range, by contacting the same withbauxite at of line 3, introduced into bauxite treating zone elevatedtemperatures which vary over a-rela and passed downwardly throughreaction n tively wide temperature range. In these operaand Withdrawn bymeans of line 9. The retions it has been found that, providing thetemaction being exo h r the mpe e nd perature of the bauxite-treatingoperation be to r se- In a c d w y P 81119211 controlled within arelatively narrow critical quantities Of a liquid are introduced at a Dtemperature range, not only will the petroleum a ty of points t eacti e5 by e s oils be desulfurized in an efllcient and economof lines 7 and pc ve y T e treated ical manner, but the treated feed stock will have 40oil withdrawn from reaction zone 5 by means of unexpected, desirableproperties which could not a lin 9 y e u th dl d r r fin d in y b.foreseen from di l ur s in th prior rt, manner desirable. It is to beunderstood that These improvements apparently are secured by auxite c na tin zone 5 may mpris any suita chemical rearrangement of themolecules, such able be and a a e of Contacting as isomerization,dehydrogenation, and perhaps units- The process of the present inventionmay be widely varied. The invention essentially com prises desulfurizinga petroleum oil by passing --.the same through a bauxite-treating zoneand volume of bauxite per hour.

may be any desired particle size. I have found it is desired to controlthe temperature within a narrow critical temperature range. Theinvention is particularly applicable in bauxite. desulfurization ofcracked petroleum feed oils boiling in the motor fuel boiling range.

In these operations, it is desirable that the temperature in thereaction zone be controlled in the range from about 600 F. to 900 F.,preferably in the range from about 750 F.' to 820 F. The operation, ingeneral, is conducted under substantially non-cracking conditions. Thus,when treating high refractory stocks, the desulfurization operation maybe conducted at temperatures as high as 900 F. without securing anysubstantial cracking of the feed oil.

The cooling fluid added at a plurality of stages may be varied widely.The cooling fluid, however, preferably comprises water in the liquid orvaporous state. A particularly desirable cooling fluid comprises wetsteam. In general, we have found that it is preferred to introduce thewater at at least three stages, and to introduce approximately 0.1% ofwater by weight, or 0.5% of steam by weight, based upon the feed oil.Particularly desirable results are secured by utilizing a plurality ofthermostats or equivalent means in the path of flowing vaporsimmediately preceding the respective points of introduction of thecooling fluid, in a manner adapted to regulate and control the flow ofthe cooling fluid introduced at the particular point.

The bauxite preferably comprises a native aluminum hydroxide containingfrom 50% to 70% of A120: and from to of water. In general, it ispreferred that the bauxite be activated by burning the same at atemperature in the range from about 500 F. to 1100 F., preferably at atemperature in the range from about 600 F. to 900 F. The feed rates mayva y considerably depending upon the general operating conditions, thecharacter of the feed oil being treated, as well as upon the type ofbauxite employed. In general, the feed rates are in the range from about1 volume to 10 volumes of oil per volume of bauxite per hour. Thepreferred rates are from about 2 to 4 volumes of oil per The bauxitealso that granular bauxite is desirable.

In order to illustrate the invention further, the following exampleis'given which should not be construed as limiting the same in anymanner whatsoever:

Example Various operations were conducted in which cracked feed oils,having a gravity of 60 A. P. I. and which boiled in the motor fuelboiling range,

Amount of water or steam injected at a plurality of stages into thereactor to give an average catalyst temperature of 800 F.

What I claim as new and wish to protect by Letters Patent is as follows:

1. Process for removing objectionable sulfur compounds from petroleumoils, which comprises passing the petroleum oil in the vaporous statethrough a bed of bauxite, and removing the heat of reaction by theintroduction of a cooling fluid comprising water at a plurality ofstages, the

total amount of water introduced being not j greater than about 0.5%based upon the quantity of oil being treated per unit of time.

2. Process as defined by claim 1, in which said petroleum oil is acracked petroleum naphtha boiling in the motor fuel boiling range, andin which said petroleum oil is contacted with the bauxite at atemperature in the range from about 600 F. to 900 F.

3. Process for removing objectionable sulfur compounds from petroleumoils, which comprises passing the petroleum oil in the vaporous statethrough a bed of bauxite, and removing the heat of reaction by theintroduction of wet steam at a plurality of points, the total amount ofwater introduced being not greater than about 0.5% based upon thequantity of oil being treated per unit of time.

4. Process as defined by claim 3, in which petroleum oil comprises acracked naphtha boiling in the motor fuel boiling range.

5. Method of controlling the temperature of a treating process, in whicha mineral oil is treated by passing the same through a bed of bauxitecatalyst and exothermic heat is thereby evolved, which comprisesintroducing water as a cooling fluid into the catalyst at a plurality ofpoints, the

total amount of water introduced being not greater than about 0.5% basedupon the quantity of oil being treated per unit of time.

6. Method as defined by claim 5, in which the treating process comprisesa desulfurization reaction. I

'7. Method as defined by claim 5, in which about 0.1% of liquid water isintroduced into the catalyst.

8. Method as defined by claim 5, in which about 0.5% of steam isintroduced into the catalyst.

9. The process as defined by claim 1. in which the water is introducedin at least three stages and in which the amount of water introducedinto each stage is thermostatically controlled so that the temperaturewithin the catalyst bed is maintained at about 600 to about 900 F.

GERALD E. PHILLIPS.

